Oxidation of 4,7-phenanthroline derivatives

Abstract

Oxidation of 1,3-diphenyl-4,7-phenanthroline with potassium permanganate in alkaline medium results in transformation of the 4,7-phenanthroline ring system into 1,8-diaazafluorenone. Oxidation of 12-aryland 12-aryl-9, 9-dimethyl-8,9,10,12-tetrahydro-7H-benzo[b][4,7]phenanthrolin-11-ones (condensation products of 6-arylmethylene-aminoquinolines with 1,3-cyclohexanedione and dimedone) with sodium nitrite in acetic acid leads to 12-aryl-9,10-dihydro-8H-benzo[b] [4,7]phenanthrolin-11-ones. 13-Aryl-7,13-dihydro-12H-indeno-[2,1-b][4,7]phenanthrolin-12-ones obtained by reaction of 6-arylmethyleneaminoquinolines with 1,3-indandione are oxidized to 13-aryl-12H-indeno[2,1-b][4,7]phenanthrolin-12-ones on heating in nitrobenzene.

Development of the catalytic synthesis of compounds of the quinoline series (the N. S. Kozlov reaction) (Review)*

“…With the aim of bringing new derivatives of 4,7-phenanthroline into the oxidation reaction we first studied the chemical behavior of 1,3-diphenyl-4,7-phenanthroline during the action of potassium permanganate when heated in an alkaline solution of KOH [55]. 2,4-Diphenyl-1,8-diazafluoren-9-one (38) was obtained with a yield of 36% as the only product instead of the expected 1,3-diphenyl-4,7-phenanthroline-5,6-dione (39), diphenyl-substituted 3,3'-bipyridyl-2,2'-dicarboxylic acid, or 3,3'-bipyridyl.…”

“…The condensation of amines of the 1-and 2-naphthylamine and 5-and 6-quinolylamine series with aromatic and heteroaromatic aldehydes, and 1,3-cyclohexanedione or its derivatives (dimedone, phendione, 5-methyl-, 5-(p-methoxyphenyl)-, 5-(p-butoxyphenyl)-, and 5-(2-furyl)-1,3-cyclohexanedione) takes place in a solution of aliphatic alcohol in the absence of a catalyst, the role of which is played by the proton of the enolized form of the β-diketone. As a result of the reaction oxo compounds of tetracyclic structure with an azaphenanthrene (benzo[f]quinoline or phenanthroline) fragment are formed [71][72][73][74][75][76].…”